Substituted 1 3-dioxolanes

ABSTRACT

A NEW COMPOUND IS DISCLOSED WHICH IS 4-ETHOXYCARBONYL-1,3-DIOXOLANE HAVING THE FOLLOWING FORMULA:   4-(C2H5-OOC-)-1,3-DIOXOLANE   IT IS USEFUL IN MAKING POLYMERS.

United States Patent 3,657,277 SUBSTITUTED 1,3-DIOXOLANES Lars-Olof Ryrfors, Perstorp, Sweden, assignor to Perstorp AB, Perstorp, Sweden N0 Drawing. Filed Sept. 16, 1970, Ser. No. 72,808 Claims priority, application Sweden, Oct. 2, 1969, 13,610/69 Int. Cl. C07d 13/04 U.S. Cl. 260340.9 1 Claim ABSTRACT OF THE DISCLOSURE A new compound is disclosed which is 4-ethoxycarbonyl-l,3-diox0lane having the following formula:

CHzOH-COOC2H5 It is useful in making polymers.

The present invention relates to new, substituted 1,3- dioxolanes intended to be used as components in polymers and having the formula where R=CH CH CH OCOCH or COOC H At the production of the new, substituted 1,3dioxolanes, 4 (3 acetoxypropyl) 1,3-dioxolane and ethoxycarbonyl 1,3 dioxolane according to the invention, pentane-LZ-S-triol and glyceric acid ethyl ester respectively are used as a starting material. Said starting material is reacted with formaldehyde or a formaldehyde dissipating compound, such as paraformaldehyde, by heating to boiling in a solvent in the presence of an acid catalyst. Then, a dioxolane ring is obtained by help of the OH-groups in 1,2-position in the starting compound. In order to get 4-(3-acetoxypropyl)-1,3-dioxolane another reaction step is necessary to modify the substituent on the dioxolane ring obtained.

Benzene is a suitable solvent, but other organic solvents, such as cyclohexane, toluene, chloroform and hexane can be used.

The acid catalyst is suitably paratoluenesulfonic acid,

but other acids, e.g. H 80 HCl, H PO and an acid ion 0 EXAMPLE 1 Production of 4-(3-acetoxypropyl)-1,3-dioxolane 4-(3-acetoxypropyl)-1,3-dioxolane 3,657,277 Patented Apr. 18, 1972 120 g. (1 mole) pentane-l,2,5-triol, 33 g. (1 mole) 92 percent paraformaldehyde and 19 g. (0.1 mole) p-toluenesulfonic acid were mixed with 1500 ml. benzene and reflux boiled under water trap for 2 hours. The benzene phase was neutralized and evaporated. The remaining oil was distilled and gave 42 g. 4-(3-propanol)-l,3-dioxolane having a boiling point of -82 C. at a pressure of 1 mm. Hg. The yield was 32 percent of the theoretical one.

66 g. (0.5 mole) 4 (3-propanol)-l,3-dioxolane were dissolved in 71.4 g. (0.7 mole) acetic anhydride and 7.8 g. (0.1 mole) pyridine and heated to 70 C. for 60 minutes. Then, the solution was evaporated. The remaining oil was distilled and resulted in 80 g. 4-(3-acetoxypropyl)- 1,3-dioxolane having a boiling point of 50 C. at a pressure of 0.02 mm. Hg. The yield was 92 percent of the theoretical one.

EXAMPLE 2 Production of 4-ethoxycarbonyl-1,3-dioxo1ane Reaction step CHzCH-COOC2H5 CHg-CHCO OC2H5 OH OH 0 0 glyceric acid ethyl ester CH:

4-ethoxycarbonyl-1,3-dioxolauo 74 g. (0.6 mole) glyceric acid ethyl ester, 21.4 g. (0.6 mole) 84 percent paraformaldehyde, 6 g. (0.03 mole) ptoluenesulfonic acid and 100 ml. benzene were mixed and reflux boiled under water trap, until no more water escaped. The benzene phase was neutralized with Ha CO and evaporated. The remaining oil was distilled and gave 70 g. of 4-ethoxycarbonyl-1,3-dioxolane having a boiling point of 8589 C. at a pressure of 3 mm. Hg. The yield was 86 percent of the theoretical one.

The substituted 1,3-dioxolanes according to the invention can be homopolymerized, copolymerized, block polymerized and graft polymerized. The comonomers which can be cationically polymerized are especially suitable, e.g. cyclic formals and cyclic ethers. Then, for example polyoxymethylenes and polyethylene oxides can be obtained. By graft polymerization or block polymerization, a large number of combinations with other materials can be obtained.

What is claimed is:

1. A substituted 1,3-dioxolane characterized by the following formula:

oHP-( JEPO o 0 02m 0 0 References Cited Chemical Abstracts, vol. 70, 1969, col. 37213f, (abstract of French Patent No. 502,385, Nov. 18, 1967).

ALEX MAZEL, Primary Examiner J. H. TURNIPSEED, Assistant Examiner U.S. Cl. X.R. 26088.3, 823 

